Reaction products of wax-anhydride compounds and polyamines

ABSTRACT

Wax-anhydride compounds and derivatives thereof, including amides, esters, etc.; processes by which they are prepared; and uses thereof, including their use as carbon paper inks, polishes, etc.

This application is a continuation of our application Ser. No. 107,569,filed Jan. 18, 1971, now abandoned, which is a division of applicationserial No. 607,877, filed Jan. 9, 1967, now U.S. Pat. No. 3,590,076,patented June 29, 1971, which is in turn a continuation-in-part ofapplication Ser. No. 527,075, filed Feb. 14, 1966, now abandoned.

This invention relates to wax-anhydrides, equivalents thereof,derivatives thereof, processes by which they are prepared, and usestherefor.

These are illustrated by the following formulae where R is the waxmoiety: ##STR1## where n is, for example 1-5, or even 25 or more incertain instances.

The wax-maleic compounds may also contain one or more of the above typeunits.

Stated another way, the wax molecule may have one or more maleic unitsattached thereto; said maleic units, which may be attached to one ormore positions on the wax molecule, may be attached directly to the waxmolecule or to one or more other maleic molecules.

In addition, derivatives thereof can also be prepared, for exampleesters, amides, ester-amides, imides, salts, etc. and poly-derivativesthereof, such as polyesters, polyamines, poly-salts, etc. Salts may beprepared from any of the above compounds which contain acidic or basicgroups.

The term "wax-maleic compound" relates to the reaction of wax or a waxsubstitute with maleic anhydride, or equivalents or derivatives thereof.It also includes derivatives of the wax-maleic reaction.

The term "maleic compound" relates to maleic anhydride, maleic acid,maleic type anhydrides or acids and derivatives thereof.

Any suitable wax or wax substitute can be employed in preparing the waxanhydride. These include microcrystalline waxes, such as plastic andtank bottom derived microcrystalline waxes, solvent extractedmicrocrystalline waxes, etc., wax substitutes such as Fischer-TropschWax, polyalkylenes such as polyethylene, polypropylene, and blendsthereof, etc.

The preferred type of hydrocarbon waxes employed are those having amelting point of about 150°-270° F. but preferably about 150°-220° F.and a penetration as defined by ASTM Test Method D5-25 of from about 0+to about 50", for example 0+ to about 30, but preferably 0+ to about 10with an optimum of 0+ to about 5. These are obtained using 100 g. totalweight for 3 seconds at 66° F. Waxes found within this range aremicrocrystalline wax, Fischer-Tropsch wax, certain of the polyalkylenessuch as polyethylenes, etc. In general, these waxes have an average ofover about 40 carbons, but preferably over about 45 carbons permolecule, such as from 50-75 or 100 or more. Where the waxes are of alower molecular weight, they should be blended with a higher molecularweight material to give this average.

All of these waxes are well known. For example they are described inU.S. Pat. No. 2,890,125, which is by reference incorporated into thepresent application.

A unique class of polyethylenes which can be employed in this inventionare those prepared by employing a catalyst which is an organolithiumcompound with a chelating tertiary amine, such as described for examplein U.S. Pat. No. 3,206,519 and in the Journal of Organic Chemistry 29,2928 (1964).

Because of its commerical importance, maleic anhydride is employed toillustrate this invention. Examples of other acids or anhydrides whichmay be reacted include citraconic acid, ethylmaleic acid, glutaconicacid, itaconic acid, methylitaconic acid, etc. The term "wax-maleiccompound" and "maleic compound" includes these acids, anhydrides andderivatives.

Although the wax-maleic compounds can be prepared by any suitablemethod, we have prepared these compositions by reacting wax with maleicanhydride under free radical forming conditions. In one embodiment, wax,maleic anhydride and a peroxide are reacted at a temperaturesufficiently high to promote free radical formation. Since heat promotesfree radical formation, a temperature sufficiently high to promote thedecomposition of the peroxide, without causing decomposition ofreactants and products, is employed. Depending on the peroxide,temperatures of about 100°-250° C., such as about 125° to 225°, forexample about 150° to 215°, but preferably about 170° to 200°, areemployed. The temperature should be sufficiently high to keep allreactants in solution or in a molten state.

In the case of di-tert-butyl peroxide the best yields are obtained inthe ranges of about 100° to 250° C., but preferably about 170° to 200°C.

Reaction times will depend on various factors such as for example on theparticular reactants, reaction conditions, etc. A reaction timesufficient to effect the desired degree of reaction completion isemployed. Ordinarily, reaction times of from about 0.5 to 6 hours, suchas about 1 to 5 hours, for example about 1.5 to 4.5 hours, butpreferably about 2 to 4 hours are employed. Shorter or longer times maybe employed to push the reaction to the desired degree of completiondepending on various factors such as reactants, conditions, peroxides,etc.

Any suitable free-radical producing agent capable of forming reactivesites can be employed. These include peroxides, hydroperoxides, etc.,for example benzoyl peroxide, acetyl peroxide, 2,4-dichlorobenzoylperoxide, tert-butyl peroxide, tert-butyl hydroperoxide, methyl benzylhydroperoxide, cumene hydroperoxide, peracetic acid, tert-butylpermaleic acid, lauryl peroxide, methyl ethyl ketone peroxide, dicumylperoxide, di-tert-butyl diperphthalate, tert-butyl peracetate, and thelike.

Other sources of free radicals besides peroxides can also be employed,for example high energy ionizing irradiation, etc., cobalt inconjunction with hydroperoxides, inorganic peroxy compounds such aspersulfates, hydrogen peroxide, etc., azo compounds of the generalformula R--N═N--R such as azobenzene, azomethane,azobisisobutyronitrile, etc., acyl-aryl nitrosoamides such asnitrosoanilide, etc.

The wax anhydrides can be prepared by the process described in U.S. Pat.No. 3,030,387 which is by reference incorporated into this application.This application is illustrated by claim 9 which states:

"A process for the preparation of alkyl hydrocarbon and cycloalkylhydrocarbon substituted succinic acid anhydrides which comprisesreacting one mole of maleic anhydride with more than one mole ofhydrocarbon selected from the group consisting of alkyl and cycloalkylhydrocarbons of from 6 to 32 carbon atoms at a temperature above 100° C.and in the presence of a catalytic amount of di-tertiary-butyl peroxide."

The hydrocarbons employed in U.S. Pat. No. 3,030,387 are liquids andsoft solids and therefore do not yield the improved products of thisinvention. In contrast the hydrocarbons employed in this invention arehard solids having high melting points and low penetrations.

All of the specific examples in U.S. Pat. No. 3,030,387 describereactions carried out with a large excess of hydrocarbon in a closedvessel. In preparing the wax-anhydrides of the present inventionsubstantially equimolar amounts or slight excesses or more ofhydrocarbons can be employed by adding maleic anhydride to thehydrocarbon at atmospheric pressure under free radical conditions.

In one embodiment maleic anhydride and the peroxide, preferably as asolution, are added to molten well-stirred wax and the reaction allowedto react to completion. The product is precipitated by pouring into aliquid in which the desired product is insoluble, and the by-productsare soluble, such as methanol, and the wax separated therefrom by anysuitable means such as by filtration, etc. Thereafter the product iswashed with methanol and collected by filtration.

In another embodiment, the maleic half-ester is converted to theanhydride in situ.

The following examples are presented by way of illustration and not oflimitation:

EXAMPLE 7 (PROCESS I)

This example illustrates the formation of a wax-maleic anhydride adduct.

A solution of 16 g. of maleic anhydride and 3 g. of di-t-butyl peroxidein 100 ml. of o-dichlorobenzene is added during two hours to 100 g. ofFischer Tropsch wax having a m.p. of 212° F. and a penetration of 4stirred and heated at 185° C. The mixture is stirred for an additionaltwo hours at 185° C., then successively cooled to 90° C. and slowlypoured into 500 ml. of stirred methanol to precipitate the wax. Themixture is filtered and the filter cake is slurried in 500 ml. of hotmethanol for 1 hour and then filtered. The washing operation is repeatedand the final solid product is air dried for about fifteen hours. Theproduct is melted and slabbed. The yield of adduct is 108 g. It had anacid number of 51 and a saponification number of 99.

EXAMPLE 8 (PROCESS II)

This example illustrates the preparation of a wax-maleic half-esteradduct which is converted in situ to the anhydride.

Isopropyl maleate is formed by adding sixty grams (one mole) ofanhydrous isopropyl alcohol during 15 minutes to 98 g. (one mole) ofstirred, molten (65° C.) maleic anhydride. The mixture is stirred for anadditional 15 minutes and then cooled to ambient temperature.

A solution of 26 g. of isopropyl maleate and 3 g of di-t-butyl peroxideis added during two hours to 100 g. of Fischer Tropsch wax having a m.p.of 212° F. and a penetration of 4, rapidly stirred and heated at 185° C.under a nitrogen atmosphere. The mixture is stirred for an additional0.5 hour at 185° C., then successively cooled to 120° C. and slowlypoured into 500 ml of rapidly stirred methanol. The mixture is heated toreflux, stirred for one hour and filtered hot (55° C.). The filter cakeis reslurried in 500 ml. of refluxing methanol for one hour and thenfiltered hot. The filter cake is melted in a 110° C. oven and thenslabbed. The product has an acid number of 46 and a saponificationnumber of 97.

Since other examples are similarly prepared, in order to save repetitivedetails, other examples are presented in the following Table I.

                                      Table I                                     __________________________________________________________________________    Initial Wax          Molar         Wax-Maleic                                                 Pene-                                                                              Ratio         Product                                                    tra- Maleic        Analyses                                                   tion Anhydride                                                                            Process                                                                              Acid                                                                              Sap.                                   Ex. Type   M.P. No.  to wax Employed                                                                             No. No.                                    __________________________________________________________________________    1   Micro- 190- 3    1.3     I     47  88                                         crystal-                                                                             195° F.                                                         line                                                                          M.W. 700                                                                  2   "      "    "    1.2     I     45  91                                     3   "      "    "    1.2     I     50  96                                     4   "      "    "    1.0    II     52  98                                     5   "      160- "    1.2    II     48  94                                                165° F.                                                     6   "      "    "    1.2    II     47  93                                     7   Fischer                                                                              212° F.                                                                     4    1.3     I     51  99                                         Tropsch                                                                       M.W. 800                                                                  8   "      "    "    1.3    II     46  97                                     9   "      202° F.                                                                     1    1.0    II     48  95                                     10  Poly-  102° C.                                                                     3    1.5     I     54  99                                         ethylene                                                                      M.W. 1500                                                                 11  Micro- 190- 3    1.0     I     46  92                                         crystal-                                                                             195° F.                                                         line                                                                          M.W. 700                                                                  12  Poly-  102° C.                                                                     3    1.4    II     47  95                                         ethylene                                                                      M.W. 1500                                                                 __________________________________________________________________________

The molecular weights of the products of this invention can be increasedby reacting the wax-maleic compound with polyfunctional compoundscapable of reacting with maleic derived moiety in the form of the acid,ester, anhydride, etc. For example, by reacting with polyamines,polyols, etc., one is able to polymerize two or more wax-maleic units.These are illustrated by the following where R is the wax moiety and R'is the moiety of the polyfunctional compound. ##STR2##

It will be noted that the above are true polymers having repetitiveunits.

In addition to forming a repetitive polymeric unit, the polyfunctionalderivative may increase molecular weight by coupling with only onecarboxylic group of each maleic unit to form a product having unreactedcarboxylic acid groups to yield a product having a plurality ofwax-maleic units bridged by the polyfunctional moiety. These areillustrated by the following:

In the case of the polyhydroxyl compound n is preferable 2-4 but mostpreferably 3. All the hydroxyl groups are preferably coupled and R' isthe moiety derived from the polyfunctional compound such as ahydrocarbon group, e.g. alkylene, arylene, etc. ##STR3## and so on,depending on the number of hydroxy groups in the polyol.

Analogous compositions may be prepared from polyamines. This results inthe formation of amides instead of esters, and amino groups in place ofhydroxy groups. In the case of polyamines, n is preferably 2-3 and mostpreferably 2. All of the amino groups are preferably coupled. ##STR4##

Polyamines may also be employed to couple wax-maleic units by formingpolyimides or both imide and amides, for example, as follows: ##STR5##

Corresponding compounds are also formed from hydroxyl amines asillustrated below. In the case of the hydroxyl amine, n is preferably2-4, but most preferably 2. All of the hydroxyl and amino groups arepreferably coupled. ##STR6##

EXAMPLE 13 (PROCESS III)

This Example illustrates the conversion of the wax-maleic half ester tothe wax-maleic anhydride, followed by coupling with a poly-functionalcompound to yield a triester:

A solution of 19 g of isopropyl maleate and 3 g of di-t-butyl peroxideis added during 2 hours to 100 g of Fischer Tropsch wax stirred andheated at 120° C. under a nitrogen atmosphere. No solvent is employed inthis example. The mixture is stirred for an additional 0.5 hour at 185°C. and then cooled to 115° C. During reaction the ester is converted tothe wax-maleic anhydride in situ. Five grams of trimethylol propane isthen added to the stirred wax-maleic adduct heated at 115° C. Themixture is stirred for three hours at 115° C. and then slabbed. ##STR7##

EXAMPLE 18

The process of Example 13 was repeated except that 2 grams of ethylenediamine was employed in place of trimethylol propane. This example 18illustrates coupling with polyamines to yield a product of the formula##STR8##

By further heating one may form the polyimide ##STR9##

EXAMPLE 25

One hundred grams of the wax-maleic compound of Example 8 was heated to150° C. for four hours to convert the material to the anhydride. Theanhydride derivative is heated and stirred at 120° C. and 1% ethylenediamine based on wax is added. Heating and stirring is continued for anadditional hour and then cooled to give a light tan, hard product,having a formula similar in structure to that of Example 18.

EXAMPLE 26

The above process was repeated except that tetraethylene pentamine wasemployed. The reaction mixture was heated to 120° C. for a period ofabout one hour, after which a reduced pressure of 200 mm was employed.The product was primarily the imide.

Since other examples are similarly prepared, in order to save repetitivedetails, other examples are presented in the following Table II.

                  TABLE II                                                        ______________________________________                                                            Mole Ratio Coupling Agent,                                Ex.  Initial Wax    Maleic/Wax % (wax basis)                                  ______________________________________                                        13   Fischer Tropsch                                                                              0.9        Trimethylol                                         MW 800                    propane, 5                                     14   Fischer Tropsch                                                                              0.9        Polyethylene                                        HW 800                    glycol- Mol. wt.                                                              600, 6                                         15   Fischer Tropsch                                                                              0.9        Ethylene                                            MW 800                    glycol, 3.5                                    16   95% Fischer Tropsch                                                                          0.9        Trimethylol                                         MW 800                    propane, 5                                          5% Polyethylene                                                               Mol. wt. 2000                                                            17   Fischer Tropsch                                                                              0.9        Glycerol, 4                                         MW 800                                                                   18   Fischer Tropsch                                                                              0.9        Ethylene                                            MW 800                    diamine, 2                                     19   Fischer Tropsch                                                                              0.9        Ethanolamine,                                       MW 800                    1.5                                            20   Fischer Tropsch                                                                              0.9        m-phenylene                                         MW 800                    diamine, 2                                     21   Microcrystalline                                                                             0.9        Trimethylol                                         Wax   MW 700              propane, 5                                     22   Polyethylene   0.9        Trimethylol                                         MW 2000                   propane, 5                                     23   Polyethylene   0.9        Ethylene                                            MW 2000                   diamine, 2                                     24   Microcrystalline                                                                             0.9        m-phenylene                                         Wax   MW 700              diamine, 2                                     25   Fischer Tropsch                                                                              1.3 (Ex.8) Ethylene                                            MW 700                    diamine, 1                                     26   Fischer Tropsch                                                                              1.3 (Ex. 8)                                                                              Tetraethylene                                       MW 700                    Pentamine, 1                                   The above waxes have the following properties:                                Fischer Tropsch mp 212° F., penetration 4                              Polyethylene mp 102° C., penetration 3                                 Microcrystalline wax mp 190-5° F., penetration 3                       ______________________________________                                    

The percent of polyfunctional coupling agent is weight percent based oninitial wax.

A wide variety of polyalcohols may be employed as coupling agents. Theseinclude glycols and other polyols.

The glycols which may be employed herein can vary widely. In general,they are the glycols conventionally employed in preparing polyesters.Suitable examples include the following: alkylene glycols of the formulaH(OA)_(n) OH where n is for example 1-10 or higher and A is alkylene:ethylene, propylene, butylene, etc., for example ethylene glycol,diethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol, triethylene glycol, butylene glycol, tetramethylene glycol,neopentyl glycol, 2-methyl-1,3-pentanediol, 1,5-pentanediol,hexamethylene glycol, etc.

The polyols used herein can be widely varied and are those containing atleast three esterifiable hydroxyl groups. In general, these are thepolyhydric alcohols conventionally employed in preparing polyesters.Illustrative examples of such alcohols are glycerol, polyglycerol,pentaerythritol, mannitol, trimethylolpropane, trimethylolethane,1,2,6-hexanetriol, poly-pentaerythritol, polyallyl alcohol,polymethallylalcohol, polyols formed by the condensation of bisphenolswith epichlorohydrin, and the like.

In addition to the aliphatic glycols and/or polyols, one may also employaromatic glycols and polyols including those of the phenolic type, forexample those of the formula HO-- A-- OH when A is an aromaticcontaining radical for example ##STR10## where R is for example,hydrocarbon, amino, amide, ester, oxygen, silicon, ketone, phosphorus,sulfur, sulfone, sulfoxide, etc. These aromatic groups may also besubstituted, for example, as follows: ##STR11## where A is a substitutedgroup for example, alkyl, alkoxy, halo, nitro, etc. and n is a number,for example, 0-4 inclusive. Also included are aromatic-containingglycols and polyols containing aliphatic groups between the aromaticgroup and the hydroxy group for example: ##STR12## etc., where R has thesame meaning as above.

The aromatic groups in the above polyol and glycol may also be in thereduced or partially reduced form. A wide variety of polyamines can alsobe employed as coupling agents.

The polyamines employed include those of the following formula:##STR13## where n is for example 1 - 8 or greater, where A is a divalentradical, for example straight or branched ##STR14## and m is for example2-10 or greater. These include the following: ##STR15##

Other examples include the following alkylated polyamines for example ofthe formula ##STR16## where the R's are H or a substituted group, suchas cycloalkyl, alkyl, alkenyl, alkynyl, aryl, etc. The preferable typeis of the formula ##STR17##

Examples include the following: ##STR18##

Aromatic polyamines can also be employed, for example: ##STR19##derivatives thereof for example, alkyl, alkoxy, halo, etc. derivatives.

Thus, any polyamine capable of reaction, whether aliphatic,cyclo-aliphatic, aromatic, heterocyclic, etc., can be employed.

In addition, one may employ polyfunctional compounds having differentreacting groups, for example both alcohol and amino groups such asalkanol amines, aromatic hydroxy amines, etc.

    (NH.sub.2).sub.n A -- (OH).sub.m

such as where A is

1. (--CH₂ --)_(x) such as where x is 1 - 10 or greater, ##STR20## 3.cycloaliphatic, etc.

Typical examples include alkanol amines, ethanol amine, propanol amine,butanol amine, decanol amine, etc. ##STR21##

In addition to the formation of polymers and coupled derivatives byreacting the wax-maleic compound with polyfunctional derivatives such aspolyalcohols, polyamines, etc., to form amides, esters, esteramides,polyimides, polyimide amides, etc., other derivatives can also be formedincluding salts, etc.

In addition the wax-maleic compounds can be reacted with monofunctionalderivatives to form corresponding esters, amides, imides, salts, etc.

For example, the wax maleic compound of this invention can be reactedwith ammonia or amines to yield salts, amides, imides or combinations ofthese groups. In the case of monoamines, these include acylatable aminesof the formula ##STR22## where R is a substituted group and R' ishydrogen or a substituted group. Examples of R and R' include alkylgroups such as methyl, ethyl, propyl, butyl, amyl, hexyl, etc.,including both straight and branch chain compounds, of the C_(n) H_(2n)₊₁ series; cycloalkyl groups such as cyclohexyl, etc.; alkenyl,alkadienyl; aryl groups, such as phenyl, etc.

In addition, even though a polyamine may be reacted, it is possible tocontrol the reaction so that only one maleic moiety is reacted, forexample to yield ##STR23##

The following illustrates the reaction of wax anhydrides with monoamines and ammonia.

EXAMPLE A

One hundred grams of the wax-maleic compound of Example 8 was heated at150° C. for 4 hours to convert the material to the anhydride. Theanhydride derivative is heated and stirred at 120° C. and 2% anilinebased on wax is added. Heating and stirring is continued for anadditional hour and then cooled to give a light tan, hard product.

EXAMPLE B

The above process was repeated except that cyclohexylamine was employed.The reaction mixture was heated to 120° C. for a period of about onehour, after which a reduced pressure of 200 mm was employed. The productwas primarily the imide.

EXAMPLE C

One hudred grams of the wax-maleic derivative of Example 8 was heated at150° C. for 4 hours to convert the material to the correspondinganhydride derivative. Heating was continued at 150° C. and a slow streamof ammonia was blown through the wax for 1 hour. Upon cooling theproduct solidified to a light brown hard solid, which was useful as acarbon paper wax.

EXAMPLE D

The process of Example A was repeated except that 3% of lauryl amine wasemployed -- R--NH₂ where R is lauryl to yield the monoamide.

Esters can also be prepared from monoalcohol R'OH where R' is alkyl suchas methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., including bothstraight and branch chain compounds, of the C_(n) H_(2n) ₊ 1 series,cycloalkyl such as cyclohexyl, etc.; alkenyl, alkadienyl; aryl groups,such as phenyl, etc. These are illustrated by the following equations:##STR24##

The formulas presented herein are idealized structures and are presentedto illustrate the probable structures of the products. Variations inthese structures may occur to yield other products or mixtures thereof.Thus, we do not wish to be bound by such structures -- rather they areused to present probable structures when the components are reacted. Forexample, where the wax-maleic formula is specified as ##STR25## or arelated formula is employed, it ideally represents a wax-maleiccompound. N in the above relates to the amino-derived moiety.

USE IN CARBON PAPER INKS

This section deals with the utilization of the wax-maleic compounds ofthis invention in carbon paper inks. There are several articles,patents, and other published literature which discuss various types ofcarbon paper, particularly in regard to formulation of the variousingredients, test procedures, utilization of various waxes, etc. See,for example, U.S. Pat. No. 2,426,248, dated Aug. 26, 1947, to Sugarman;Chapter 12 entitled "Carbon Paper and Other Duplicating Papers" by R. R.Wissinger in the book edited by R. H. Mosher entitled "SpecialtyPapers", published by the Chemical Publishing Co., New York in 1950; thepaper on the "Rheology of Carbon Paper Inks" by E. S. Gale and B. J.Staneslow in the American Ink Maker issue of December 1950; the paper on"Converting of Carbon Papers" by F. M. McFarland in the Paper TradeJournal, Volume 137, pages 230-237 (1953); and the book Commercial Waxesby H. Bennett, pages 368, 377 and 429-431, published by ChemicalPublishing Co., New York, in 1944.

We have particularly found that the wax-maleic compounds which have beencoupled with polyamines such as for example diamines yield superiorcarbon paper inks. Thus, we have discovered that coupled compounds ofthe formula ##STR26## yield superior inks, where R is the wax moiety,and R' is the polyamine derived moiety preferably hydrocarbon and mostpreferably aliphatic or aromatic, and n is at least 2, such as 2-4 orgreater, but preferably 2.

Although the uncoupled wax-maleic compounds yield excellent inks, thecoupled derivatives are superior, particularly in regard to oilretention penetration.

There are many different types of carbon paper and related materials inuse today. The three most widely used types of carbon paper are theone-time carbon which is used once and then thrown away, the pencilcarbon which may also be used once, or may be used many times, and thetypewriter carbon. The one-time carbon is the most widely used type ofcarbon paper and it finds wide application in business and multipleforms and other applications. In the production of one-time carbonpaper, cost is all important. On the other hand, for typewriter carbons,quality rather than cost is important, and for pencil carbons, cost andquality are intermediate in importance.

The carbon paper ink may be viewed simply as a mixture containing a wax,an oil, a pigment and a dye. The oil serves as the vehicle and thepigment and dye give the color and some of the body. Most of thedesirable characteristics in the finished ink must be supplied by thewax and these will be described later. Other materials may also be usedin carbon paper to give it certain properties. For example, petrolatummay be used as part or all of the vehicle to impart certain propertiessuch as plasticity and toughness, and paraffin wax may be used as asubstitute for part of the wax to give a cheaper formulation. One of theunique properties of many of the wax-maleic compounds of this inventionis that they are able to carry a lot of paraffin wax into the inkformulation without detracting greatly from the desirablecharacteristics required. In this respect, these products are comparableto Carnauba and Ouricury and superior to Montan. Other materials may beused in carbon paper inks such as clay to cheapen the formula, oleicacid which acts as a dye solubilizer, rubbers to give toughness,dispersing agents, etc.

The consistency and other properties of the ink can be varied to acertain degree by the choice of the oil which is used. For example,various oils ranging from a relatively light mineral oil (100 SUS at100° F.) up to heavy oils and petrolatums may be used. These oils andpetrolatums may be colorless or range in color up to black. The darkercolored materials are generally better dispersants for the pigment.

There are numerous pigments which may be used in typical formulations.The most common pigment is carbon black and this comes in numerousgrades such as channel blacks, furnace blacks, etc., and each of thesegrades come in many modifications. The channel blacks are, in general,the most desirable as far as quality is concerned, but on the otherhand, they are also the most expensive. The high-grade channel blackshave an oxygenated surface which aids in its dispersion and which canabsorb the dye and other materials. As one goes down the scale of carbonblacks, lesser amounts of this very desirable oxygenated surface areencountered. Blue pigments may also be used, such as Milori Blue, andothers, as can many other blue pigments. Numerous other colored pigmentsmay also be used as described in the literature.

Many dyes are commonly employed in carbon paper inks. The common onesare Methyl Violet, Nigrosine, Victoria Blue, etc., and salts of thesematerials. It is advantageous to use a dye which is soluble in the wax,but if this is impossible, a solubilizer must be used. One of theadvantages of using the wax-maleic compounds of this invention is thatthe dye is soluble in the wax and no solubilizer is necessary. Ingeneral, any solubilizer, which is used will detract from the qualitiesof the finished ink, i.e., will cause dye bleed, soften the ink, causefrosting, etc. In some instances it is possible to completely eliminatethe dye, but this is the exception rather than the rule.

A wax to be useful for this purpose, must have many specific propertieswhen used in small concentration in the finished ink; for example, inconcentrations of from 8% to 12% in one-time carbon paper inks, or inhigher percentages, up to 30% or 40%, in typewriter carbons.

It seems that most of the desirable characteristics required in aone-time carbon paper ink must be imparted by small percentages of wax.This is particularly true of one-time carbon paper inks. Since thesewaxes must have so many specific characteristics, which seem to bespecific for only Carnauba and Ouricury wax, it is not surprising thatthese two natural waxes are widely used as one of the components ofcarbon paper inks and that there are no synthetic materials which cancompletely replace these materials in the percentages in which they areused. It was quite surprising that many of the products of thisinvention have a combination of all the desirable characteristicsrequired and that the materials served as complete replacements for theexpensive natural waxes, Carnauba and Ouricury in many applications andin some respects these waxes are actually superior to the two naturalwaxes.

To be useful for carbon paper inks a wax must be able to dissolve thedye, such as methyl violet, Victoria blue, nigrosine, etc., preferablywithout the addition of a solubilizer, such as oleic acid. In thisrespect, the waxes of this invention are much superior to the naturalwaxes Carnauba, Ouricury, and Montan which are almost universally usedin one-time carbons. A wax must also produce good flow in a one-timecarbon paper ink so that a thin uniform coating can be obtained. Toproduce good flow, a wax should give an ink of low viscosity, nothixotropy and no yield value (be newtonian). The dispersion of thecarbon black and the viscosity of the wax are the important variableswhich influence the flow of the finished ink. The ability of a wax todisperse carbon can be measured by the procedure described by Gale andStaneslow in the aforementioned article. If a wax gives B-typedispersion or better, at 6%, no flow difficulties would be expected.Also, in this respect, many of the products of this invention are equalto or superior to the natural waxes Ouricury, Carnauba and Montan.

A wax must also yield a finished ink which is hard and which will notbleed oil. These properties can be easily tested, at least to a certaindegree, by determining the oil retention penetration and the oilretention of a wax oil blend. In this respect, the waxes of thisinvention show great value and are comparable, in some cases superior,to Carnauba, Ouricury and Montan which is a property which is often sohard to duplicate.

The follwing are formulations employing wax-maleic compositions of thisinvention for a one-time carbon of medium intensity:

    ______________________________________                                        Carbon Paper Ink 1                                                            A.  Grams      Material                                                       ______________________________________                                            12         A product of this invention (Ex. 25)                               20         Paraffin Wax (m.p. approx. 135° F.)                         17         Carbon Black                                                        1         Methyl Violet                                                      50         Mineral Oil                                                    B.  Same as A except that the product of Example 18 was                           employed, in place of Example 25.                                         ______________________________________                                    

The paraffin wax used is a high-melting-point paraffin and the oil is a100-second oil at 100° F. The carbon black can be a channel black suchas exemplified by Peerless Beads or a cheaper channel black such asRaven 15, manufactured by Columbian Carbon Company, or a furnace blackas exemplified by Statex B-12 manufactured by Columbian Carbon Company.

The above formulations may be modified in several ways to give differentintensities and grades of ink; for example clay can be substituted forsome of the carbon black and oil to cheapen the formula without greatlyimpairing quality, and other variations in the proportions of wax may bemade.

A similar one-time carbon paper formulation employing clay is asfollows:

    ______________________________________                                        Carbon Paper Ink 2                                                            A.  Grams      Material                                                       ______________________________________                                            12         A product of this invention (Ex. C)                                25         Paraffin Wax (m.p. approx. 135° F.)                         0.5        Methyl Violet Base                                                 1          Nigrosine                                                          18         ASP-100 clay                                                       10         Carbon Black                                                       17         300 Sec. Mineral Oil                                               16.5       Petrolatum                                                     B.  The above example was repeated except that the                                product of Example 20 was employed, in place of - Example                 ______________________________________                                            C.                                                                    

One type of carbon black which may be used is a channel black such asPeerless Beads or a cheaper channel black such as Raven 15 or comparableproducts, or mixtures of these. These waxes also find use in other typesof carbon paper and ribbons such as pencil carbons, typewriter ribbons,etc. A typical one-time medium blue pencil carbon formulation is asfollows:

    ______________________________________                                        Carbon Paper Ink 3                                                            A.  Grams      Material                                                       ______________________________________                                            12         A product of this invention (Ex. 25)                               25         Paraffin Wax (m.p. approx. 135° F.)                         18         ASP-100 clay                                                       20         Milori blue                                                        13         300 sec. Mineral Oil                                               12         Petrolatum                                                     B.  The above example was repeated except that the                                product of Example 18 was employed, in place of - Example                 ______________________________________                                            25.                                                                   

A typical typewriter formulation is as follows:

    ______________________________________                                        Carbon Paper Ink 4                                                            A.  Grams      Material                                                       ______________________________________                                            25         A product of this invention (Ex. C)                                18         Carbon black ("Raven 15")                                           1         Methyl Violet                                                      10         Paraffin Wax (m.p. approx. 135° F.)                         16         300 sec. Mineral Oil                                           B.  The above example was repeated except that the product                        of Example 20 was employed, in place of Example C.                        ______________________________________                                    

As above, these formulations may be modified in many ways to obtaincarbon paper ink to fit individual uses.

These inks may be prepared either in a ball mill or a three-roll mill byconventional procedures using temperatures of from approximately 190° F.to 220° F. Care must be taken when certain dyes are used not to exceedthese temperatures; otherwise, the dye will decompose. These finishedinks can be coated onto paper using a Mayer type coater or comparableequipment. Normally, it is best to apply approximately 2.5 lbs. of waxper ream for one-time carbons and higher quantities for typewritercarbons.

Among the properties which are highly desirable in carbon paper waxesare oil retention penetration and carbon dispersion. The properties aretested as follows:

Oil Retention Penetration Test

Twenty-five grams of wax on test and 25 g. of a 100 SUS mineral oil(i.e., Texaco Ink Oil No. 538) are placed in a 150 ml beaker which iscovered by a watch glass and placed in an oven at 100° C. for 2 hours.Stir the sample with a glass rod, pour it into an aluminum foil dish(Fisher Scientific Company Cat. No. 8-732) resting on asbestos, and thencover with a 600 ml beaker. Allow the sample to stand for 1 hour at roomtemperature, then transfer to a water bath at 25.0° + or - 0.2° C. andhold for 3-4 hours. Penetration values are then obtained on the top andbottom of the sample, and these values are averaged to give the oilretention penetration. Penetration values are determined under a testload of 100 g. for 5 seconds, and are reported to the nearest tenth of amillimeter. The penetration needle employed is similar to that describedin ASTM test method D 1321-54T except that the length of taper is 23 mm.rather than 6.5 mm.

Carbon Dispersion Test

One to two and one-half grams (4-10%) of wax on test and 20.5-19.0 g.(82-76%) of a 100 SUS oil (i.e. Texaco Ink Oil No. 538) are heated withstirring at 95°-100° C. in a 500 ml round bottom flask until a solutionis obtained. Add 3.5 g (14%) of a carbon black such as Kosmos 40 (UnitedCarbon Company) and approximately 20 g. of 3 mm. diameter glass beads.Stir at 95°-100° C. for 30 minutes using a stirrer which scrapes thewidth of the flask. A drop of the prepared ink hs then placed on a hotstage heated to 95° C., or on an adsorption cell through which aglycerol-water solution is circulated at 95° C. Place a cover glass overthe sample, press with tweezers or small spatula to form a thin,semi-transparent film, then examine under a microscope at ×200, bothunder stress and without stress. The inks are then classified as Type A(no structure under or without stress), type B (no structure understress, structure without stress), type C (structure under or withoutstress), and type D (pigment not wetted). Type A is the best followed bytypes, B, C, and D. This test is well described in the paper on the"Rheology of Carbon Paper Inks" by E. S. Gale and B. J. Staneslow,published in the American Ink Maker issue of December, 1950.

The following amine reaction products prepared in the manner of Example18 were tested for oil retention penetration at weight ratios of 50%wax-maleic-amine product and 50% oil, according to the above method. Thewax employed in each case was a Fischer Tropsch wax.

                  TABLE III                                                       ______________________________________                                        Weight                                                                        % Amine                                                                              Amine Employed in                                                      Based  Fischer Tropsch-Maleic-                                                                       50/50 Reaction Product/Oil                             on Wax Amine Reaction Product                                                                        Oil Retention Penetration                              ______________________________________                                        3      Ethylene Diamine                                                                              25                                                     2      Ethylene Diamine                                                                              33                                                     2.5    Ethylene Diamine                                                                              29                                                     1.5    Ethylene Diamine                                                                              36                                                     9      Aniline         60                                                     6      Ethylene Diamine                                                                              43                                                     6      Ethanol Amine   47                                                     3      Ethanol Amine   43                                                     4      Diaminopropane  31                                                     3      Diaminopropane  33                                                     8      Morpholine      40                                                     6      Morpholine      47                                                     4      p-Phenylene Diamine                                                                           45                                                     3      p-Phenylene Diamine                                                                           43                                                     6      p-Phenylene Diamine                                                                           37                                                     5      p-Phenylene Diamine                                                                           37                                                     4      m-Phenylene Diamine                                                                           37                                                     3      m-Phenylene Diamine                                                                           33                                                     6      m-Phenylene Diamine                                                                           36                                                     5      m-Phenylene Diamine                                                                           36                                                     4      o-Phenylene Diamine                                                                           67                                                     3      o-Phenylene Diamine                                                                           64                                                     6      o-Phenylene Diamine                                                                           66                                                     5      o-Phenylene Diamine                                                                           66                                                     ______________________________________                                    

Employing the above carbon dispersion test all of the above productswere classified as Type B or better.

OTHER USES

This section deals with other uses for the wax-maleic compounds of thisinvention.

Because of their very desirable properties, particularly in reference totheir excellent hardness, they are useful for blending with othermaterials to impart their favorable properties, for example; they may beblended in small concentrations with paraffinic type waxes to yieldblends with improved hardness and increased melting point. One specificapplication in this line would be to blend 3-10% of the hard productsdescribed in this application with paraffin wax to yield a product withbetter blocking characteristics.

One of the important uses for these products is for various types ofpolishes; for instance, floor polish, shoe polish, furniture polish, andautomobile polish.

A typical formulation in which these products have found use in thefield of emulsion floor polishes is as follows:

    ______________________________________                                        Floor Polish A                                                                 Grams      Material                                                          ______________________________________                                        50          The product of this invention (Ex. 7)                             50          "Durez 219"                                                       10          Oleic Acid                                                         6          2-amino-2-methyl-1-propanol                                        4          Borax                                                             830         Water                                                             ______________________________________                                    

The first three ingredients in the above formulation are blended attemperature up to but not exceeding 350° F. The mixture is cooled to210° F. with agitation. The 2-amino-2-methyl-1-propanol is added withstirring at 200° to 210° F. followed immediately by the borax in asaturated solution. The resulting mixture is heated with stirring at200° F. to a maximum of 210° F. for 5 minutes and then the wax melt isslowly poured into water at 200° F. with rapid agitation. When theemulsion has smoothed out, 10-20% of a cold solution of leveling agentis added during agitation and cooled to room temperature. A levelingagent which may be used is a 12% ammoniacal shellac solution prepared bydissolving 102 g of refined dewaxed shellac in a solution of 26 g of26°Be (28%) ammonia in 722 g. of water.

"Durez 219" is a terpene-phenolic, oil soluble, high melting, lowviscosity, thermoplastic resin having a melting poilt (capillary) of130°-136° C., an acid number of from 60 to 70, a specific gravity at 25°C. of 1.09 and a refractive index of 1.552. It is manufactured andsupplied by the Durez Plastic and Chemicals Division of HookerElectrochemical Co.

Many modifications of the above formulation can be made; for instance,the resin can be eliminated or other resins substituted for the above.Other waxes can be used in conjunction with the above or the products ofthe other examples in this invention can be used.

We have particularly found that the wax-maleic compounds which have beencoupled with polyhydroxy compounds such as glycols and polyols yieldsuperior emulsified wax polishes. Thus we have discovered that coupledcompounds of the formula: ##STR27## yield superior emulsified waxpolishes where R is the wax moiety, R' is the polyhydroxyl derivedmoiety, preferably hydrocarbon and most preferably aliphatic, and n isat least 2, such as 2-6 or greater but preferably 3.

Although uncoupled wax-maleic compounds yield excellent emulsifiedwaxes, the coupled derivatives are superior particularly in regard totheir recoatability, i.e. the ability to apply an additional layer ofemulsified wax without deleteriously effecting the layers of wax alreadyapplied.

Floor Polish B

This is an example of a typical formulation of an emulsion floor polishin which the coupled wax-maleic compound is employed.

    ______________________________________                                        Floor Polish B                                                                  This is an example of a typical formulation of                              an emulsion floor polish in which the coupled wax-maleic                      compound is employed.                                                         ______________________________________                                        Grams           Material                                                      ______________________________________                                         25             Product of Ex. 13                                              1              Tributoxyethyl phosphate                                       3              Diethylamino ethanol                                          200             Water                                                         ______________________________________                                    

The first two components in the formulation are melted at 230° F.Diethylaminoethanol is added to the melt and the mixture is stirred andaged for five minutes and then added slowly to the water at 205° F. withrapid agitation. When the addition is completed the emulsion is cooledrapidly to ambient temperature.

These polishes, when spread on linoleum, asphalt tile, rubber tile,vinyl tile, etc. yields a film which when dried is very hard, scuff andabrasion-resistant, with a high gloss and with good water resistance.Polish B had superior recoatability.

The above Floor Polish B formulation was prepared with the followingproducts -- Example 14, 15, 16 and 17 to yield excellent polishes.

A good no-rub automobile polish and furniture polish can be preparedfrom the following formulations and procedures:

    ______________________________________                                        Automobile Polish                                                             A.   Grams      Materials                                                     ______________________________________                                             3.0        A product of this invention (Ex. 8)                                3.6        Silicone (5000 cs. visc.)                                          3.6        Oleic Acid                                                         1.7        Morpholine                                                         67.5       Mineral Spirits (boiling point 275-325° F.)                 40.0       Water                                                         B.   The above formulation was also prepared with the                              product of Example 13 in place of Example 8.                             ______________________________________                                    

The wax, silicone and oleic acid are dissolved in the mineral spiritsand an emulsion formed. A suitable 5000 cs. viscosity silicone would beLinde L-41 diethyl silicone oil sold by Linde Air Products Co., Divisionof Union Carbide and Carbon Corporation.

These last two formulas make good high-gloss polishes of the no-rub,quick-drying type. Most silicone polishes require thorough cleaning ofthe surface of application for best results. With clean surfaces thepolish is spread smoothly, allowed to dry to a powdery film and the filmwiped off, leaving a high gloss with no rubbing.

The ratio of silicone to wax should be maintained while the variation inthe total solids (wax in silicone) is between four and ten percent.

Following is a formulation for the manufacture of a shoe polish waxemploying a wax of this invention:

    ______________________________________                                        Shoe Polish                                                                   A.   Grams      Material                                                      ______________________________________                                             12         Paraffin Wax (131-133° F.)                                  13         A wax of this invention (Ex. 1)                                    15         Turpentine                                                         60         Mineral Spirits                                               B.   The above polish was also prepared with the product                           of Example 13 in place of Example 1.                                     ______________________________________                                    

The first two ingredients are melted together and to this blend the lasttwo materials are added. After a solution is obtained, the polish ispoured at a temperature just above the point in which the wax starts toseparate. Depending upon the color of the finished product, any ofseveral dyes may be used, the main criteria being that of solubility.

In any of these formulations, oftentimes other products from thisinvention other than those specifically mentioned may be used, butgenerally in these cases, slight modifications may become necessary.These modifications can be made without too much difficulty by those whoare skilled in the art. The above formulations are very good startingpoints and these formulas can be altered or modified in any of manyways.

The above are examples of uses for the wax-maleic compounds of thisinvention. In addition, they can be used in place of, or in conjunctionwith, other waxes.

We claim:
 1. A wax-maleic compound coupled with a polyfunctionalpolyamine selected from the group consisting of1. a polyamine of theformula ##STR28## said wax-maleic compound having a wax molecule moietyto which at least one maleic compound unit is attached, (1) said maleiccompound being selected from the group consisting of maleic acid, maleicanhydride, citraconic acid, citraconic anhydride, ethyl maleic acid,ethyl maleic anhydride, glutaconic acid, glutaconic acid anhydride,itaconic acid, itaconic acid anhydride, methylitaconic acid andmethylitaconic acid anhydride and (2) said wax being selected from thegroup consisting of plastic microcrystalline waxes, tank bottommicrocrystalline waxes, solvent extracted microcrystalline waxes,Fischer-Tropsch waxes, and mixtures thereof, having a melting point ofat least 150° F. and a penetration of from about 0+ to about 50 (ASTMTest Method D5-25), the molar ratio of (1) to (2) being from about 1.0to about 1.5.
 2. The product of claim 1 wherein the polyamine is NH₂ CH₂CH₂ NH₂.
 3. The product of claim 1 wherein the polyamine isphenylenediamine.
 4. The product of claim 1 wherein the polyamine is##STR29##
 5. The product of claim 3 wherein phenylenediamine ismetaphenylenediamine.
 6. The product of claim 5 wherein the wax is amicrocrystalline wax.
 7. The product of claim 5 wherein the wax is aFischer-Tropsch wax.
 8. The product of claim 1 wherein the wax is amicrocrystalline wax.
 9. The product of claim 1 wherein the wax is aFischer-Tropsch wax.
 10. The product of claim 1 wherein said wax-maleiccompound is the product obtained by reacting said maleic compound withsaid wax at substantially atmospheric pressure under free radicalconditions.
 11. The product of claim 1 wherein said wax-maleic compoundis the product obtained by reacting a half ester of said maleic compoundwith said wax at substantially atmospheric pressure under free radicalconditions.